The kinetic model previously established for describing the thermal oxidation of polymethylenic substrates has been successfully generalized to a series of six epoxy-diamine networks (EPO-DA) characterized by very different glass transition temperatures. This model is derived from the so-called “closed-loop” mechanistic scheme which consists in a radical chain reaction initiated by the decomposition of hydroperoxides and propagating via the C-H bonds located in α of heteroatoms (N and O). The numerous model parameters were determined by applying a “step by step” procedure combining experiment and simulation. On the one hand, oxygen transport properties (i.e. coefficients of oxygen diffusion and solubility) were estimated from a compilation of literature data. On the other hand, rate constants and formation yields were determined by inverse solving method from the measurements of oxygen consumption and carbonyl build-up performed on six different EPO-DA networks between 25 and 200 °C and between 0.16 and 20 bars of oxygen partial pressure in our laboratory or in the literature. It was found that the molecular mobility mainly affects the rate constants of the elementary reactions involving the reactive species in the lowest concentration, i.e. peroxy radicals. In fact, the rate constant k₆ of the apparent termination of peroxy radicals is reduced by about five orders of magnitude when passing from rubbery to glassy state due to the freezing of large amplitude cooperative molecular movements. In contrast, the rate constant k₃ of the propagation of oxidation, involving peroxy radicals but also the polymer substrate, is only changed by one order of magnitude around the glass transition temperature. The introduction of the effect of molecular mobility into the Arrhenius laws of k₆ and k₃ allows building master curves and finally, proposing a single kinetic model for the whole family of EPO-DA networks.

先前建立的用于描述聚亚甲基基体热氧化的动力学模型已成功地推广到一系列六个环氧二胺网络（EPO-DA），其特征是玻璃化转变温度非常不同。该模型源于所谓的“闭环”机制方案，该方案包含自由基链反应，该自由基链反应由氢过氧化物的分解引发，并通过位于杂原子（N和O）的α中的CH键传播。通过应用结合实验和模拟的“逐步”程序确定了众多模型参数。一方面，从文献数据的汇编中估计了氧气的输送特性（即氧气扩散系数和溶解度）。另一方面，速率常数和地层产率是通过逆求解法，根据我们实验室中在25至200°C和氧分压在0.16至20 bar之间的六个不同EPO-DA网络上进行的耗氧量和羰基积累量的测量而确定的在文学中。已经发现分子迁移率主要影响涉及最低浓度的反应性物质即过氧自由基的基本反应的速率常数。实际上，速率常数k 已经发现分子迁移率主要影响涉及最低浓度的反应性物质即过氧自由基的基本反应的速率常数。实际上，速率常数k 已经发现分子迁移率主要影响涉及最低浓度的反应性物质即过氧自由基的基本反应的速率常数。实际上，速率常数k₆过氧自由基的表观终止是由大约5个数量级从橡胶状到玻璃态传递由于大振幅合作分子运动冻结时减小。相反，涉及过氧自由基但也涉及聚合物基质的氧化传播的速率常数k ₃在玻璃化转变温度附近仅改变一个数量级。将分子迁移率的影响引入k ₆和k ₃的阿伦尼乌斯定律中，可以建立主曲线，最后为整个EPO-DA网络家族提出一个动力学模型。